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Can donor-acceptor bonded dinuclear metallocenes exist? A computational study on the stability of CpM′-MCp (M′ = B, AI, Ga, In, Tl; M = Li, Na, K) and its isomers

Organometallics, ISSN: 0276-7333, Vol: 26, Issue: 27, Page: 6839-6843
2007
  • 10
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  • 3
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  • Citations
    10
    • Citation Indexes
      10
  • Captures
    3

Article Description

Recently, a series of dinuclear metallocenes CpM′-MCp connected by a donor-acceptor interaction M′→M have been designed. However, an important yet unresolved issue is whether the donor-acceptor bonded metallocenes can be intrinsically stable toward isomerization since such a simple combination might result in various isomeric forms. Therefore, in this paper, we investigate the stability toward isomerization of a series of donor-acceptor dinuclear metallocens CpM′-MCp (M′ = B, Al, Ga, In, Tl; M = Li, Na, K) at the DFT level. We find that the σ-type donor-acceptor sandwich form CpM′-MCp (A) can be the ground-state isomer only for M′ = B. For M′ = Al, Ga, In, Tl, the previously unconsidered π-type donor-acceptor sandwich form M′Cp-MCp (B), in which Cp in CpM′ acts as a donor and M acts as an acceptor, is more stable. Moreover, the classical isomer R E-ERR′ is very important for the homonuclear group 13 compounds; the classical isomer CpM′Cp-M (F) in sandwich form plays only a minor role except for cis-CpBCp-Li, which is nearly isoenergetic with the σ-type donor-acceptor isomer CpB-LiCp. Finally, Cp*M′ (Cp* = methyl-substituted cyclopentadienyl group) will significantly stabilize the σ-type donor-acceptor isomer relative to the classical one, yet has little influence on the energy differences between the σ- and π-type donor-acceptor isomers. Therefore, our results should provide useful guides for future synthetic effort aimed at the other donor-acceptor bonded dinuclear metallocenes. © 2007 American Chemical Society.

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